The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Experimental studies of oxygen isotope fractionation in the carbonic acid system at 15°, 25°, and 40°C

In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO₃⁻ and CO₃²⁻ concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO₃⁻, CO₃²⁻, and CO_2(aq)) were investigated at 15°, 25°, and 40°C. To investigate oxygen isotope exchange between HCO₃⁻, CO₃²⁻, and H₂O, NaHCO₃ solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl₂ was added to the NaHCO₃ solutions. This resulted in immediate BaCO₃ precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon (DIC). Data from experiments at 15°, 25°, and 40°C (1 atm) show that the oxygen isotope fractionation between HCO₃⁻ and H₂O as a function of temperature is governed by the equation:

     

The Ah receptor in marine animals: phylogenetic distribution and relationship to cytochrome P4501A inducibility

In mammals, the induction of cytochrome P4501A forms by chlorinated dibenzo-p-dioxins, chlorinated dibenzofurans, and halogenated biphenyls is under control of a soluble protein known as the Ah (aromatic hydrocarbon) receptor. Little is known about the presence and properties of the Ah receptor in other vertebrate and invertebrate species. In these studies, we sought evidence for an Ah receptor in the liver or liver-equivalent of 20 species of marine and freshwater animals, using the photoaffinity ligand 2-azido-3-[¹²⁵I] iodo-7,8-dibromodibenzo-p-dioxin (N₃[¹²⁵I]Br₂DD). Specific labeling of cytosolic proteins by N₃[¹²⁵I]Br₂DD was observed in seven species of teleost and elasmobranch fish, in PLHC-I fish hepatoma cells, and in beluga whales. No specifically labeled proteins were found in cytosol from two species of agnathan fish nor in any of nine invertebrate species representing eight classes of four phyla. The presence or absence of specifically labeled polypeptides corresponds with the inducibility of cytochrome P4501A and sensitivity to the toxic effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin and related planar halogenated aromatic hydrocarbons in many of these groups. Thus, Ah receptor function may have arisen early invertebrate evolution and has been conserved from elasmobranch and teleost fish to mammals.     

Comparison of cytochrome P450 in three butterflyfish species: Ecological implications of elevated CYP2B and CYP3A in Chaetodon capistratus

The relationship between cytochrome P450 and feeding on terpenoid-rich gorgonian corals was investigated in a species of tropical butterflyfish and compared with two other sympatric congeners that do not feed on gorgonians. Fish were collected from non-polluted waters in Belize and the levels of two cytochrome P450 isozymes (CYP2B and CYP3A) were immunoquantitated in addition to quantification of total P450. Chaetodon capistratus regularly feeds on gorgonian corals and has higher levels of total hepatic microsomal cytochrome P450 than C. ocellatus or C. striatus. The content of hepatic P450 (0.588–0.794 nmol mg⁻¹) in C. capistratus is among the highest ever reported in teleosts from non-polluted waters and is significantly greater than detected in C. ocellatus or C. striatus. Chaetodon capistratus also had a larger hepatic index (g liver per g fish) and more microsomal protein (mg protein per g liver), factors that translate into 3.3- to 8-fold more total P450 per g fish. Sexual differences in total P450 were observed between male and female C. capistratus, but not among the other species. The contents of proteins detected by immunoassay with polyclonal anti-scup P450B (CYP2B) and anti-human P4503A (CYP3A) were 2- to 10-fold and 2- to 20-fold greater, respectively, in C. capistratus than in the congeneric species. CYP2 and CYP3 gene families in mammals are thought to have evolved partially in response to dietary allelochemicals. These results suggest that these P450 isozymes may also be important in marine teleosts that feed on terpenoid-rich prey.     

Beneficiation and digestion of Georgia offshore phosphates

Abstract

The U.S. Bureau of Mines conducted beneficiation and digestion tests to evaluate the potential of recovering P₂O₅ from an apatite deposit located 10 nautical miles offshore Savannah, GA, in the Exclusive Economic Zone (EEZ). A 1.8 metric ton sample containing 1.0–1.5% P₂O₅ was obtained in a cooperative drilling project involving the Bureau of Mines, the Marine Minerals Technology Center‐Continental Shelf Division, the Minerals Management Service, and the Georgia Nonenergy Minerals Offshore Task Force. Beneficiation methods were evaluated with the goal of producing a 29–31% P₂O₅ concentrate with a CaO: P₂O₅ratio of less than 1.6: 1. These specifications were obtained using a combination of gravity separation and flotation. Comparative leaching tests conducted using EEZ, Idaho, and Florida phosphate concentrates showed that these EEZ phosphates behaved similarly to land‐based phosphates. The results suggest that as land‐based phosphate deposits are depleted, ocean phosphates represent a feasible alternate source.     

Large-scale laboratory experiment on erosion of sand beds by moving circular vertical jets

This study investigates the topographic deformation due to the erosion of a sand bed impinged by a moving submerged turbulent round jet in a large-scale laboratory. The test conditions represent the case of discharges beneath a vessel while operating in water with a limited clearance such as a shallow navigation channel. The jet moves horizontally and discharges water vertically downward towards the bed. The distance between the jet nozzle and the bed equals six times the jet diameter so the jet flow is in the potential core region. The speed of the jet horizontal motion was varied to examine its effect on the scour profile. The characteristic lengths of the scour profile in the asymptotic state were determined by modifying the empirical formulas in Aderibigbe and Rajaratnam [1996. Erosion of loose beds by submerged circular impinging vertical turbulent jets. Journal of Hydraulic Research 34(1), 19–33]. The maximum scour depth, the scour hole radius, and the ridge height were found to be a function of the ratio of the jet exit to jet translation velocities and were modeled using a hyperbolic function. Empirical equations describing the scour profile were developed and the scour profile was found to be self-similar when normalized by appropriate length scales.